Use of metal complex compounds comprising pyridine pyrimidine or s-triazine derived ligands as catalysts for oxidations with organic peroxy acids and/or precursors of organic peroxy acids and h202

Abstract

The invention accordingly relates to the use as catalysts of at least one metal complex of formula (1) [L n Me m X p ] z Y q (1), wherein all substituents have the meanings as defined in the claims for oxidation reactions with organic peroxy acids and/or precursors of organic peroxy acid and H 2 O 2 , as well as to novel detergent compositions.

1 . A method of oxidizing an oxidizable substrate which comprises bringing an oxidizable substrate into contact with at least one metal complex of formula (1)
   [L n Me m X p ] z Y q   (1),   
     wHerein
 Me is manganese; titanium; iron; cobalt; nickel or copper, 
 X is a coordinating or bridging radical, 
 n and m are each independently of the other an integer having a value of from 1 to 8, 
 p is an integer having a value of from 0 to 32, 
 z is the charge of the metal complex, 
 Y is a counter-ion, 
 q=z/(charge of Y), and 
 L is a ligand of formula (2) 
 
     
       
         
         
             
             
         
       
     
     wherein
 Q 1  is N or CR 10 , 
 Q 2  is N or CR 11 , 
 R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10  and R 11  are each independently of the others hydrogen; 
 unsubstituted or substituted C 1 -C 18 alkyl or unsubstituted or substituted aryl; cyano; halogen; nitro; —COOR 12  or —SO 3 R 12  wherein
 R 12  is in each case hydrogen, a cation or unsubstituted or substituted C 1 -C 18 alkyl or unsubstituted or substituted aryl; 
 
 —SR 13 ; —SO 2 R 13  or —OR 13  wherein
 R 13  is in each case hydrogen or unsubstituted or substituted C 1 -C 18 alkyl or unsubstituted or substituted aryl; 
 
 —NR 14 R 15 ; —(C 1 -C 6 alkylene)-NR 14 R 15 ; —N ⊕ R 14 R 15 R 16 ; —(C 1 -C 6 alkylene)-N ⊕ R 14 R 15 R 16 ; —N(R 13 )—(C 1 -C 6 alkylene)-NR 14 R 15 ; —N[(C 1 -C 6 alkylene)-NR 14 R 15 ] 2 ; 
 —N(R 13 )—(C 1 -C 6 alkylene)-N ⊕ R 14 R 15 R 16 ; —N[(C 1 -C 6 alkylene)-N ⊕ R 14 R 15 R 16 ] 2 ; —N(R 13 )—N—R 14 R 15  or —N(R 13 )—N ⊕ R 14 R 15 R 16 , wherein
 R 13  is as defined above and 
 R 14 , R 15  and R 16  are each independently of the other(s) hydrogen or unsubstituted or substituted C 1 -C 18 alkyl or unsubstituted or substituted aryl, or 
 
 R 14  and R 15 , together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further hetero atoms, 
 as catalysts for oxidation reactions with organic peroxy acids and/or precursors of organic peroxy acids and H 2 O 2  and or a precursor of H 2 O 2 . 
 
   
   
       2 . A methods according to  claim 1 , wherein Me is manganese, which is in oxidation state II, III, IV or V. 
   
   
       3 . A method according to  claim 1 , wherein
 X is CH 3 CN, H 2 O, F − , Cl − , Br − , HOO − , O 2   2− , O 2− , R 17 COO − , R 17 O − , LMeO −  or LMeOO − , wherein R 17  is hydrogen or unsubstituted or substituted C 1 -C 18 alkyl or aryl, and   L and Me are as defined in  claim 1 .   
   
   
       4 . A method according  claim 1 , wherein
 Y is R 17 COO − , ClO 4   − , BF 4   − , PF 6   − , R 17 SO 3   − , R 17 SO 4   − , SO 4   2− , NO 3   − , F − , Cl − , Br −  or I − , wherein   R 17  is hydrogen or unsubstituted or substituted C 1 -C 18 alkyl or aryl.   
   
   
       5 . A method according to  claim 1 , wherein
 n is an integer having a value of from 1 to 4.   
   
   
       6 . A method according to  claim 1 , wherein
 m is an integer having a value of 1 or 2.   
   
   
       7 . A method according to  claim 1 , wherein
 p is an integer having a value of from 0 to 4.   
   
   
       8 . A method according to  claim 1 , wherein
 z is an integer having a value of from 8− to 8+.   
   
   
       9 . A method according to  claim 1 , wherein
 R 5  is C 1 -C 12 alkyl; phenyl unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, N-mono- or N,N-di-C 1 -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, N-phenylamino,   N-naphthylamino, phenyl, phenoxy or by naphthyloxy; cyano; halogen; nitro; —COOR 12  or —SO 3 R 12  
 wherein R 12  is in each case hydrogen, a cation, C 1 -C 12 alkyl, unsubstituted phenyl or phenyl substituted as indicated above; —SR 13 , —SO 2 R 13  or —OR 13    
 wherein R 13  is in each case hydrogen, C 1 -C 12 alkyl, unsubstituted phenyl or phenyl substituted as indicated above; 
   —N(R 13 )—NR 14 R 15  
 wherein R 13  is as defined above and R 14  and R 15  are each independently of the other hydrogen, unsubstituted or hydroxy-substituted C 1 -C 12 alkyl, unsubstituted phenyl or phenyl substituted as indicated above, 
 or R 14  and R 15 , together with the nitrogen atom linking them, form an unsubstituted or C 1 -C 4 alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring; 
 —NR 14 R 15  or —N ⊕ R 14 R 15 R 16  wherein R 14 , R 15  and R 16  are each independently of the other(s) hydrogen, unsubstituted or hydroxy-substituted C 1 -C 12 alkyl, unsubstituted phenyl or phenyl substituted as indicated above, 
 or R 14  and R 15 , together with the nitrogen atom linking them, form an unsubstituted or C 1 -C 4 alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring; N-mono- or N,N-di-C 1 -C 4 alkyl-N ⊕ R 14 R 15 R 16  unsubstituted or substituted by hydroxy in the alkyl moiety, 
 wherein R 14 , R 15  and R 16  are each independently of the others hydrogen, unsubstituted or hydroxy-substituted C 1 -C 12 alkyl, unsubstituted phenyl or phenyl substituted as indicated above, or R 14  and R 15 , together with the nitrogen atom linking them, form a pyrrolidine, piperidine, piperazine, morpholine or azepane ring which is unsubstituted or substituted by at least one C 1 -C 4 alkyl or by at least one unsubstituted C 1 -C 4 alkoy and/or substituted C 1 -C 4 alkyl, wherein the nitrogen atom may be quaternised; N-mono- or N,N-di-C 1 -C 4 alkyl-NR 14 R 15  unsubstituted or substituted by hydroxy in the alkyl moiety, wherein R 14  and R 15  may have any one of the above meanings. 
   
   
   
       10 . A methods according to  claim 1 , wherein L have the following formula (3) 
     
       
         
         
             
             
         
       
     
     wherein
 R′ 3  and R′ 7  are independently from each other hydrogen; C 1 -C 4 alkoxy; hydroxy; N-mono- or N,N-di-C 1 -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, wherein the nitrogen atoms, especially the nitrogen atoms that are not bonded to one of the rings A, B and/or C, may be quaternised; or a pyrrolidine, piperidine, piperazine, morpholine or azepane ring unsubstituted or substituted by at least one C 1 -C 4 alkyl, wherein the amino groups may be quaternised, 
 R′ 5  is C 1 -C 4 alkoxy; hydroxy; N-mono- or N,N-di-C 1 -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, wherein the nitrogen atoms, especially the nitrogen atoms that are not bonded to one of the rings A, B and/or C, may be quaternised; or a pyrrolidine, piperidine, piperazine, morpholine or azepane ring unsubstituted or substituted by at least one C 1 -C 4 alkyl, wherein the amino groups may be quaternised. 
 
   
   
       11 . A methods according to  claim 10 , wherein L have the following formula (3) 
     
       
         
         
             
             
         
       
     
     wherein
 R′ 3  and R′ 7  are independently from each other hydrogen; C 1 -C 4 alkoxy; hydroxy; N-mono- or N,N-di-C 1 -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, wherein the nitrogen atoms, especially the nitrogen atoms that are not bonded to one of the rings A, B and/or C, may be quaternised; or a pyrrolidine, piperidine, piperazine, morpholine or azepane ring unsubstituted or substituted by at least one C 1 -C 4 alkyl, wherein the amino groups may be quaternised, 
 R′ 5  is C 1 -C 4 alkoxy; hydroxy; N-mono- or N,N-di-C 1 -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, wherein the nitrogen atoms, especially the nitrogen atoms that are not bonded to one of the rings A, B and/or C, may be quaternised; or a pyrrolidine, piperidine, piperazine, morpholine or azepane ring unsubstituted or substituted by at least one C 1 -C 4 alkyl, wherein the amino groups may be quaternised, 
 
     with the proviso that
 (i) at least one of the substituents R′ 3 , R′ 5  and R′ 7  is one of the radicals 
 
     
       
         
         
             
             
         
       
       wherein R 15  and R 16  are independently from each other hydrogen or unsubstituted or substituted C 1 -C 18 alkyl or unsubstituted or substituted aryl and 
     
     wherein the unbranched or branched alkylene group may be unsubstituted or substituted, and wherein the C 1 -C 4 alkyl groups, which are branched or unbranched independently of one another, may be unsubstituted or substituted and wherein the piperazine ring may be unsubstituted or substituted. 
   
   
       12 . A methods according to  claim 1 , wherein L have the following formula (4) and/or (5) 
     
       
         
         
             
             
         
       
     
     wherein
 R′ 5  is C 1 -C 4 alkoxy; Cl; hydroxy; phenyl; phenyl substituted by OC 1 -C 2 alkyl, OH or C 1 -C 4 alkyl; N-mono- or N,N-di-C 1 -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; or —NR 14 R 15 ; —(C 1 -C 6 alkylene)-NR 14 R 15 ;
 —N(R 13 )—(C 1 -C 6 alkylene)-NR 14 R 15 ; —N[(C 1 -C 6 alkylene)-NR 14 R 15 ] 2 ; or —N(R 13 )—N—R 14 R 15 , wherein
 R 13  is hydrogen; C 1 -C 12 alkyl or unsubstituted phenyl or phenyl substituted by (substituted in the alkyl moiety by hydroxy) N-mono- or 
 N,N-di-C 1 -C 4 alkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-, phenoxy- or naphthyloxy, and 
 R 14  and R 15  are each independently of the other hydrogen, unsubstituted or hydroxy-substituted C 1 -C 12 alkyl, unsubstituted phenyl or phenyl substituted as indicated above, or 
 R 14  and R 15 , together with the nitrogen atom linking them, form a pyrrolidine, piperidine, piperazine, morpholine or azepane ring that is unsubstituted or substituted by at least one unsubstituted C 1 -C 4 alkyl and/or substituted C 1 -C 4 alkyl, especially a pyrrolidine, piperidine, piperazine, morpholine or azepane ring, and 
 
 
 R′ 3  and R′ 7  are each independently of the other hydrogen; C 1 -C 4 alkoxy; Cl; hydroxy; phenyl; phenyl substituted by OC 1 -C 2 alkyl, OH or C 1 -C 4 alkyl; N-mono- or N,N-di-C 1 -C 4 alkylamino substituted by hydroxy in the alkyl moiety; or —NR 14 R 15 ; —(C 1 -C 6 alkylene)-NR 14 R 15 , —N(R 13 )—(C 1 -C 6 alkylene)-NR 14 R 15 ; —N[(C 1 -C 6 alkylene)-NR 14 R 15 ] 2 ; or —N(R 13 )—N—R 14 R 15 , wherein
 R 13  is hydrogen; C 1 -C 12 alkyl or unsubstituted phenyl or phenyl substituted by (substituted in the alkyl moiety by hydroxy) N-mono- or N,N-di-C 1 -C 4 alkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-, phenoxy- or naphthyloxy, and 
 R 14  and R 15  are each independently of the other hydrogen; unsubstituted or hydroxy-substituted C 1 -C 12 alkyl, unsubstituted phenyl or phenyl substituted as indicated above, or 
 R 14  and R 15 , together with the nitrogen atom linking them, form a pyrrolidine, piperidine, piperazine, morpholine or azepane ring that is unsubstituted or substituted by at least one unsubstituted C 1 -C 4 alkyl and/or substituted C 1 -C 4 alkyl, especially a pyrrolidine, piperidine, piperazine, morpholine or azepane ring. 
 
 
   
   
       13 . A method according to  claim 12 , wherein L have the following formula (4) and/or (5) 
     
       
         
         
             
             
         
       
     
     wherein R′ 3  and R′ 7  are independently from each other hydrogen; C 1 -C 4 alkoxy; Cl; hydroxy; phenyl; phenyl substituted by OC 1 -C 2 alkyl, OH or C 1 -C 4 alkyl; N-mono- or N,N-di-C 1 -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, wherein the nitrogen atoms, especially the nitrogen atoms that are not bonded to one of the rings A, B and/or C, may be quaternised; or a pyrrolidine, piperidine, piperazine, morpholine or azepane ring unsubstituted or substituted by at least one C 1 -C 4 alkyl, wherein the amino groups may be quaternised,
 R′ 5  is C 1 -C 4 alkoxy; Cl; hydroxy; phenyl; phenyl substituted by OC 1 -C 2 alkyl, OH or C 1 -C 4 alkyl; N-mono- or N,N-di-C 1 -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, wherein the nitrogen atoms, especially the nitrogen atoms that are not bonded to one of the rings A, B and/or C, may be quaternised; or a pyrrolidine, piperidine, piperazine, morpholine or azepane ring unsubstituted or substituted by at least one C 1 -C 4 alkyl, wherein the amino groups may be quaternised, 
 with the proviso that 
 (i) at least one of the substituents R 13 , R 15  and R 17  is one of the radicals 
 
     
       
         
         
             
             
         
       
     
     wherein R 15  and R 16  are independently from each other hydrogen or unsubstituted or substituted C 1 -C 18 alkyl or unsubstituted or substituted aryl and 
     wherein the unbranched or branched alkylene group may be unsubstituted or substituted, and wherein the C 1 -C 4 alkyl groups, which are branched or unbranched independently of one another, may be unsubstituted or substituted and wherein the piperazine ring may be unsubstituted or substituted. 
   
   
       14 . A methods according to  claim 1  wherein at least one mono- or poly-peroxy acid having at least 1 to 20 carbon atoms in the alkyl chain and/or its corresponding precursor and H 2 O 2  is used. 
   
   
       15 . A method according to  claim 14  wherein at least one 
     organic peroxy acids of formula 
     
       
         
         
             
             
         
       
     
     wherein
 M signifies hydrogen or a cation, 
 R 18  signifies unsubstituted C 1 -C 18 alkyl; substituted C 1 -C 18 alkyl; unsubstituted aryl; substituted aryl; —(C 1 -C 6 alkylene)-aryl, wherein the alkylene and/or the Palo group may be substituted; and 
 phthalimidoC 1 -C 8 alkylene, wherein the phthalimido and/or the alkylene group may be substituted is used. 
 
   
   
       16 . A method according to  claim 15 ,
 wherein CH 3 COOOH or epsilon-phthalimido peroxy hexanoic acid or a alkali salt thereof is used.   
   
   
       17 . A method according to  claim 1 ,
 wherein TAED and/or NOBS as precursors of peroxy acids and sodium percarbonate and/or sodium perborate are used.   
   
   
       18 . A method according to  claim 1  for the bleaching of stains, bleaching of soiling on textile material, for the prevention of redeposition of migrating dyes, or for the cleaning of hard surfaces. 
   
   
       19 . A method according to  claim 1 , wherein the metal complex compounds of formula (1) are used as catalysts for reactions using peroxo acids or their precursors for bleaching in the context of paper making. 
   
   
       20 . A method according to  claim 1 , wherein the metal complex compounds of formula (1) are used in detergent, cleaning, disinfecting or bleaching compositions. 
   
   
       21 . A method according to  claim 1 , wherein the metal complex compounds of formula (1) are used in automatic dishwasher formulations. 
   
   
       22 . A method according to  claim 20 , wherein the metal complex compounds of formula (1) are formed in situ in the detergent, cleaning, disinfecting or bleaching composition. 
   
   
       23 . A detergent, cleaning, disinfecting or bleaching composition containing
 I) from 0 to 50 wt-%, A) of at least one anionic surfactant and/or B) of a non-ionic surfactant,   II) from 0 to 70 wt-%, C) of at least one builder substance,   III) 1-99 wt-%, D) of at least one peroxy acid and/or at least one precursors of peroxy acid, the latter in combination with hydrogen peroxide and/or a precursor of hydrogen peroxide.   IV) E) at least one metal complex compound of formula (1) as defined in  claim 1  in an amount that, in the liquor, gives a concentration of from 0.5 to 100 mg/litre of liquor, when from 0.5 to 20 g/litre of the detergent, cleaning, disinfecting or bleaching agent are added to the liquor, and   V) water ad 100 wt-%,   
     wherein the percentages are in each case percentages by weight, based on the total weight of the composition. 
   
   
       24 . A solid formulation containing
 a) from 1 to 99 wt-%, of at least one metal complex compound of formula (1) as defined in  claim 1  and at least one organic peroxy acid and/or at least one precursor of an organic peroxy acid and H 2 O 2 .   b) from 1 to 99 wt-%, of at least one binder,   c) from 0 to 20 wt-%, of at least one encapsulating material,   d) from 0 to 20 wt-% of at least one further additive and   e) from 0 to 20 wt-% water.   
   
   
       25 . A solid formulation according to  claim 24 , which is in the form of granules.